EP2988867A2 - Procédé - Google Patents

Procédé

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Publication number
EP2988867A2
EP2988867A2 EP14723889.3A EP14723889A EP2988867A2 EP 2988867 A2 EP2988867 A2 EP 2988867A2 EP 14723889 A EP14723889 A EP 14723889A EP 2988867 A2 EP2988867 A2 EP 2988867A2
Authority
EP
European Patent Office
Prior art keywords
compound
formula
otf
alkyl
independently selected
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14723889.3A
Other languages
German (de)
English (en)
Inventor
Andrew Phillips
Christian Grave
Gurmeet Singh BINDRA
Crystal O'CONNOR
Vsevolod KHLEBNIKOV
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University College Dublin
Original Assignee
NOVAUCD
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Filing date
Publication date
Application filed by NOVAUCD filed Critical NOVAUCD
Publication of EP2988867A2 publication Critical patent/EP2988867A2/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/184—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine mixed aromatic/aliphatic ring systems, e.g. indoline
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
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    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/002—Osmium compounds
    • C—CHEMISTRY; METALLURGY
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    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • C07F15/0046—Ruthenium compounds
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a process for the production of dihydrogen. More specifically, the invention relates to a process for catalysing the release of dihydrogen from ammonia borane, and derivatives thereof, using a transition metal catalyst.
  • the process of the invention has important applications in the field of hydrogen fuel cells.
  • Chemical hydrides can be packaged as non-pyrophoric, non-hazardous, solid, slurried or liquid fuels. Hydrogen may then be generated on demand from the chemical hydride under controlled conditions.
  • hydrogen storage materials have a high hydrogen content and a low molecular weight.
  • ammonia borane, H 3 N-BH 3 which has a very high hydrogen content by weight (19.2 %) and is attracting attention as a means of achieving efficient chemical hydrogen storage.
  • US 2009274613 discloses the production of hydrogen from ammonia borane using a catalyst complex of the formula L n -M-X, where M is a base metal such as Fe, Mn, Co, Ni and Cu, X is an anionic nitrogen- or phosphorus-based ligand or hydride, and L is a neutral ancillary ligand that is a neutral monodentate or polydentate ligand.
  • ligand stabilized homogenous catalysts containing Ru, Co, Ir, Ni and Pd to catalyse the release of hydrogen from ammonia borane is also described in WO 2008141439 (Kanata Chemical Technologies Inc.).
  • Suitable ligands include phosphines, aminophosphines, heterocyclic ligands, diaminophosphines, diamines, thiophines and thioamines.
  • US 20080159949 discloses a method of generating hydrogen from an ammonia borane complex using catalysts including cobalt complexes, noble metal complexes and metallocenes.
  • suitable noble metal catalysts include NaRhCIs, chlorotris(triphenylphosphine) Rh (I), (NH 4 ) 2 RuCI 6 K 2 PtCI 6 , (NH 4 ) 2 PtCI 6 Na 2 PtCI 6 , H 2 PtCI 6 , Fe(C 5 H 5 ) 2 and di- -chlorobis(p-cymene)chlororuthenium.
  • the method is suitable for use in polymer electrolyte membrane fuel cells (also known as proton exchange or PEMFCs).
  • JP201 1-1 16681 discloses an Fe based metal-boron complex as catalyst to dehydrogenate ammonia borane.
  • the present invention seeks to provide alternative methods of generating hydrogen. Specifically, the invention seeks to provide a means for storing hydrogen that allows for the controlled and safe release of dihydrogen at a constant rate. In a preferred aspect, the invention seeks to provide catalysts suitable for the catalytic dihydrogen decoupling of ammonia boranes that exhibit improved turnover and/or enhanced reaction kinetics compared to catalysts previously described in the art. Moreover, the present catalyst offer improved long term stability to oxygen and moisture.
  • the present invention broadly relates to a process for the catalytic dihydrogen decoupling of ammonia borane and derivatives thereof.
  • a first aspect of the invention relates to a process for the production of dihydrogen comprising contacting at least one complex of formula (I),
  • X " is an anion
  • M is a metal selected from Ru, Os, Fe, Co and Ni;
  • D is optionally present and is one or more monodentate or multidentate donor ligands;
  • Y 1 is selected from CR 13 , B and N;
  • R 3 and R 4 are each independently selected from H, C 1-6 -aIkyl, aryl and C 1-6 -haloalkyl, and a linker group optionally attached to a solid support; or
  • Y 2 is a direct single bond or double bond, or is CR 8 ;
  • R 1 , R 2 , R 5"13 and R 6 ⁇ 18 are each independently selected from H, C 1-6 -alkyl, C 2 - 6 -alkenyl, C 2 - 6 -alkynyl, aryl, C 1-6 -haloalkyl, NR 19 R 20 and a linker group optionally attached to a solid support; or two or more of said R 1" 3 and R 16 18 groups are linked, together with the carbons to which they are attached, to form a saturated or unsaturated hydrocarbon group;
  • R 14 , R 5 , R 19 and R 20 are each independently selected from H, C-,_ 6 -alkyl, C 2 - 6 -alkenyl, C 2 - 6 -alkynyl, aryl, C 1-6 -haloalkyl, and a linker group optionally attached to a solid support; with at least one substrate of formula (II)
  • R 21 R-NH-BH-R 23 R wherein R 21 to R 24 are each independently selected from H, C -6 -alkyl, fluoro- substituted C 1-6 -alkyl, C 6 . 14 -aryl and C 6-14 -aralkyl, or any two of R 21 , R 22 , R 23 and R 24 are linked to form a C 3-10 -alkylene group or C 3 _ 0 -alkenylene group, which together with the nitrogen and/or boron atoms to which they are attached, forms a cyclic group; or a substrate comprising two, three or four substrates of formula (II) linked via one or more bridging groups so as to form a dimeric, trimeric or tetrameric species, and wherein the bridging group is selected from straight or branched C -6 -alkylene optionally substituted by one or more fluoro groups; boron; C 6 .
  • the presently described process involves the use of a homogenous catalyst that activates gaseous dihydrogen.
  • Ab initio calculations and experimental evidence have shown that a bifunctional mechanism is operative for the dehydrocoupling of ammonia borane.
  • the unique dual site design of the ⁇ - diketiminato-metal complex offers the possibility for reversible H 2 coupling, thereby regenerating the original ammonia borane and eliminating the need for external removal and reloading of the energy storage medium.
  • the presently claimed catalyst system displays enhanced dehydrogenation kinetics compared to the previously described first generation systems described in WO 201 1 151792.
  • the present catalysts can be synthesized in high yield from commercially available precursors and in the solid state under N 2 stored indefinitely.
  • the catalyst-to-substrate ratio directly controls the rate of H 2 released.
  • the catalysts are capable of extracting up to two equivalents of H 2 from the ammonia borane substrate.
  • a second aspect of the invention relates to a hydrogen generation system comprising: (a) at least one complex of formula (I)
  • X " is an anion
  • M is a metal selected from Ru, Os, Fe, Co and Ni;
  • D is optionally present and is one or more monodentate or multidentate donor ligands;
  • Y 1 is selected from CR 13 , B and N;
  • R 3 and R 4 are each independently selected from H, C -6 -alkyl, aryl and C -6 -haloalkyl, and a linker group optionally attached to a solid support; or
  • Y 2 is a direct single bond or double bond, or is CR 18 ;
  • R , R Z , R 5"13 and R 16"18 are each independently selected from H, C 1-6 -alkyl, C 2-6 -alkenyl, C 2 _6-alkynyl, aryl, C 1-6 -haloalkyl, NR 19 R 20 and a linker group optionally attached to a solid support;
  • R 1"13 and R 16-18 groups are linked, together with the carbons to which they are attached, to form a saturated or unsaturated hydrocarbon group;
  • R 14 , R 15 , R 19 and R 20 are each independently selected from H, C 1-6 -alkyl, C 2-6 -alkenyl, C 2- 6-alkynyl, aryl, Ci_ 6 -haloalkyl, and a linker group optionally attached to a solid support;
  • R to R are each independently selected from H, C-i_ 6 -alkyl, fluoro- substituted Ci -6 -alkyl, C 6 . 14 -aryl and C 6 -i 4 -aralkyl, or any two of R 2 , R 22 , R 23 and R 24 are linked to form a C 3 .
  • a third aspect of the invention relates to the use of at least one complex of formula (I) as defined above in a fuel cell.
  • a fourth aspect of the invention relates to a fuel cell comprising at least one complex of formula (I) as defined above.
  • a fifth aspect of the invention relates to a method of thermolytically dehydrogenating a substrate of formula (II) as described above, said method comprising contacting at least one substrate of formula (II) with a complex of formula (I) in the presence of a solvent.
  • a sixth aspect of the invention relates to the use of at least one complex of formula (I) as defined above in a method of thermolytically dehydrogenating a substrate of formula (II) as described above.
  • a seventh aspect of the invention relates to the use of at least one complex of formula (I) as defined above in a method of producing hydrogen.
  • An eighth aspect of the invention relates to complexes of formula (I).
  • a ninth aspect of the invention relates to a method of using a hydrogen generation system as defined above which comprises modulating the hydrogen pressure in said system so as to modulate activity of the at least one complex of formula (I).
  • . n alkyl means straight or branched chain, saturated alkyl groups containing from one to n carbon atoms and includes (depending on the identity of n) methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, 2,2-dimethylbutyl, n-pentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-hexyl and the like, where the variable n is an integer representing the largest number of carbon atoms in the alkyl group.
  • the C 1-n alkyl group is a C 1-20 -aIkyl group, more preferably a Ci -6 -alkyl group, even more preferably, a C ⁇ -alkyl group.
  • the term refers to a C -n -aikyl group as defined above in which one or more hydrogens are replaced with a halogen atom selected from Br, F, CI and I.
  • the Ci-n-haloalkyl group is a group, more preferably a C-i.io-haloalkyl group, even more preferably, a C 1-6 -haloalkyl group.
  • the C -n -haloalkyl group is a Ci_ n -fluoroalkyl group, more preferably, a C -20 -fluoroalkyl group, even more preferably a C 1- 0 -fluoroalkyl group, even more preferably still, a d-e-fluoroalkyl group.
  • CF 3 is a particularly preferred C 1-6 - fluoroalkyl group.
  • C 6-n aryl means a monocyclic, bicyclic or tricyclic carbocyclic ring system containing from 6 to n carbon atoms and at least one aromatic ring and includes, depending on the identity of n, phenyl, naphthyl, anthracenyl, 1 ,2- dihydronaphthyl, 1 ,2,3,4-tetrahydronaphthyl, fluorenyl, indanyl, indenyl and the like, where the variable n is an integer representing the largest number of carbon atoms in the aryl group.
  • the C 6 - n aryl group is a C 6 .-, 4 -aryl group, more preferably, a C 6 -i 0 -aryl group, even more preferably, a phenyl group.
  • aralkyl means a conjunction of C 1-n alkyl or C-
  • the term "carbocyclic ring” means a carbon-containing ring system, that includes monocycles, fused bicyclic and polycyclic rings, bridged rings and metallocenes. Where specified, one or more carbons in the rings may be substituted or replaced with heteroatoms.
  • the carbocyclic group is cyclohexyl.
  • each of A and B is independently an unsaturated carbocyclic ring, more preferably a phenyl ring.
  • Carbocyclic ring A is substituted by groups R 9 -R 12 as defined above, whereas carbocyclic ring B is substituted by groups R 5 -R 8 as defined above.
  • fluoro-substituted means that one or more, including all, of the hydrogens in the group have been replaced with fluorine.
  • the suffix "ene” added on to any of the above groups means that the group is divalent, i.e. inserted between two other groups.
  • a first aspect of the invention relates to a process for the production of hydrogen comprising contacting at least one complex of formula (I), with at least one substrate of formula (II) as defined above.
  • the process is carried out in the presence of a suitable solvent.
  • the invention consists of a catalyzed chemical process for the controlled and safe release of hydrogen at constant rate from the substrate ammonia borane or related organic ⁇ , ⁇ -substituted derivatives.
  • the overall purpose of the process is to provide a constant flow rate of high purity hydrogen for use in fuel cells or combustion engines, which in combination with atmospheric oxygen emit only water. No external heating, light or electricity is required to initiate the catalytic dehydrogenation process.
  • Hydrogen has been shown to carry an extremely high energy to mass ratio of 120 MJ kg "1 as compared to conventional gasoline products (44 MJ kg "1 ).
  • the present applicant has synthesized a series of different derivatives of the catalytic complex. A number of these have been tested in dehydrogenation reactions under different conditions (variation of substrate, solvent, concentration, temperature) and in direct comparison to catalysts of the first generation (see, for example, WO 201 1151792). The release of over two equivalents of H 2 from ammonia borane was achieved.
  • the presently claimed invention provides a significantly improved dual site catalyst system.
  • the unique tetra-coordinating anionic diketiminato ligand leads to an immediate loss of the supporting ligand in solution, creating a large free reactive site and consequently enhanced reaction kinetics.
  • the catalytic activity of the ⁇ - diketiminato-ruthenium complex can be modified through simple changes in the ligand design. Anchoring of the catalyst to solid support is also possible, thereby facilitating easy separation of the spent materials.
  • the process of the invention uses a substrate of formula (II), R 21 R 22 NH-BHR 23 R 24 , as described above.
  • R 21 , R 22 , R 23 and R 24 are each independently selected from H, C -10 -alkyl, fluoro-substituted-C ⁇ o-alkyl, C 6 . 10 -aryl and C 6 -i 0 -aralkyl, or any two of R 21 , R 22 , R 23 and R 24 are linked to form a C 2-6 -alkylene group, which together with the nitrogen and/or boron atoms to which they are attached, forms a cyclic group.
  • R 21 , R 22 , R 23 and R 24 are each independently selected from H, C 1-6 - alkyl, fluoro-substituted-C 1-6 -alkyl, C 6 -aryl and C 6 _i 0 -aralkyl, or any two of R 21 , R 22 , R 23 and R 24 are linked to form a C 2 _ 6 -alkylene group, which together with the nitrogen and/or boron atoms to which they are attached, forms a cyclic group.
  • R 23 and R 24 are both H.
  • R 23 and R 24 are both H, and R 21 and R 22 are each independently selected from H, C 1- Q -alkyl, fluoro-substituted-C ⁇ o-alkyl, C 6 _ D -aryl and C 6 _ 10 -aralkyl, or R 21 and R 22 are linked to form a C 2 . 6 -alkylene group, which together with the nitrogen atom to which they are attached, forms a cyclic group.
  • R 23 and R 24 are both H and R 21 and R 22 are each independently selected from H, C -10 -alkyl, fluoro-substituted-C ⁇ o-alkyl and C 6 -i 0 -aryl.
  • R 21 , R 22 , R 23 and R 24 are each independently selected from H and C -2 o-alkyl.
  • R 23 and R 24 are both H, one of R 2 and R 22 is H and the other is selected from H, C 1- 0 -alkyl, C-
  • R 23 and R 24 are both H, and R 21 and R 22 are each independently selected from H, methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, tert-butyl, sec-butyl, phenyl and benzyl, CF 3 , or R 21 and R 22 are linked to form a C 2-6 - alkylene group, which together with the nitrogen atom to which they are attached, form a cyclic group.
  • the C 2 - 6 -alkylene group is a C 4 -alkylene group.
  • two of R 21 , R 22 , R 23 and R 24 are linked to form a C 2- 0 - alkylene group, which together with the nitrogen and/or boron atoms to which they are attached, forms a cyclic group.
  • the substrate of formula II is selected from the foll
  • the substrate of formula II is of formula: Compounds of this type are described in Neiner, D.; Karkamkar, A,; Bowden, M.; Choi, J. Y.; Luedtke, A.; Holladay, J.; Fisher, A.; Szymczakc, N.; Autrey, T.: Energy Environ. Sci., 2011 , 4, 4187.
  • the substrate of formula (II) is selected from ammonia borane, methylamine borane, dimethylamine borane, di-isopropylamine borane, isopropylamine borane, tert-butylamine borane, isobutylamine borane, phenylamine borane and pyrrolidine borane.
  • the substrate of formula (II) is dimethylamine borane.
  • the substrate of formula (II) is ammonia borane, H 3 B-NH 3 , i.e. R 2 , R 22 , R 23 and R 24 are all H.
  • Ammonia borane is a non- combustible, industrially inexpensive, low molecular weight solid substrate that carries multiple molecular equivalents of hydrogen. Ammonia borane has a high hydrogen carrying capacity of 19.6% per weight and is not flammable. This is consistent with the objectives set forth by the US Department of Energy of 5.5 wt% in vehicles by 2015.
  • a molecular catalyst consisting of a metal and supporting organic ligands
  • the process of the invention utilises a complex of formula (I), as defined above, as a catalyst.
  • the catalyst is a bifunctional dual site complex consisting of a transition metal and a ligand that is robust and stable over long periods of storage and reaction time.
  • the presently claimed catalysts are tethered 3 -substitued- -diketiminato or 4 -substituted- - diketiminato ruthenium complexes.
  • the presently claimed catalyst structures afford faster dehydrogenation kinetics compared to the first generation catalysts.
  • the additional benefit of this second catalyst generation can be, depending on the application, twofold: (i) to achieve a higher H 2 release rate, and/or (ii) to lower the amount of catalyst used (and consequently the cost of the system).
  • the presently claimed catalysts show a high degree of tolerance. Every catalyst is restricted by its turnover frequency, which determines the reaction kinetics and, by the amount of catalyst needed to achieve a certain rate, also the cost of the system. Any increase in the turnover number therefore represents a valuable contribution to the art.
  • the second generation of catalysts presented here excels in an increased turnover frequency.
  • the donor ligand D dissociates in solution to form the active catalytic species, although at some point re-association cannot be ruled out.
  • Some of the compounds are isolated after synthesis as a mixture of the complex with the donor ligand D and the complex where D has been lost. These mixtures can be used without further separation in the dehydrogenation experiments.
  • the donor ligand D is n, 6 -arene
  • Z 1 and Z 2 do not coordinate to M.
  • donor ligand D is absent
  • Z and Z 2 do coordinate to M.
  • X " is selected from OTf, BF 4 " , PF 6 “ , BPfV or BArF “ (B((3,5-CF3) 2 C 6 H3)4 “ ), more preferably, OTf " .
  • X " does not imply a specific bond type to the metal M.
  • X " represents any bond type between the limits of a non-coordinated anion and a coordinated ligand with formally negative charge. In other words, X " may or may not coordinate - weakly or strongly - with metal
  • M is selected from Ru, Ni and Co. More preferably, M is Ru.
  • R 5 -R 12 are each independently selected from H, methyl, CF 3 and isopropyl.
  • R-i and R 2 are both independently C 1-6 - alkyl, more preferably, methyl.
  • Y 1 is CR 13 , more preferably CH.
  • a and B are both phenyl groups, i.e. the compound is of formula (V):
  • R 1 -R 12 , D, M, Y 1 , Z 1 , Z 2 and X " are as defined above.
  • Z R 3 and Z 2 R 4 are each independently S-C 1-6 -alkyl, more preferably Z 1 R 3 and Z 2 R 4 are each independently selected from SCH 3 and SCH 2 CH 3 .
  • Z 1 R 3 is S-C 1-6 -alkyl
  • Z 2 is a direct bond
  • R 4 to R 8 are independently C 1-6 -alkyl, more preferably Z 1 R 3 is selected from SCH 3 and SCH 2 CH 3 and Z 2 is a direct bond, and R 4 and R 8 are methyl.
  • Z and Z 2 are each independently selected from S and NR 14 .
  • Z 1 is selected from S and NR 14
  • Z 2 is a direct bond
  • Z 2 R 1 and Z 1 R 2 together form the following moiety: s— i
  • the complex is of formula (Va)
  • X " is an anion selected from CI “ , Br “ , PF 6 “ , TfO “ ;
  • D is optional and is selected from (VI) and (VII),
  • Z 1 and Z 2 are each independently selected from NR 14 , PR 15 , O and S; or Z 2 is a direct bond to R 4 ;
  • R 3 and R 4 are each independently selected from H, C -6 -aIkyl, aryl and C -6 -haloalkyl, and a linker group optionally attached to a solid support; or
  • Y 2 is a direct single bond or double bond, or is CR 18 ;
  • R 1 , R 2 , R 5 13 and R 1 EM 8 are each independently selected from H, C 1-6 -alkyl, C 2 - 6 -alkenyl, C 2- 6-alkynyl, aryl, C 1-6 -haloalkyl, NR 9 R 20 and a linker group optionally attached to a solid support;
  • R 1"13 and R 16-18 groups are linked, together with the carbons to which they are attached, to form a cyclic saturated or unsaturated hydrocarbon group;
  • R 14 , R 15 , R 9 , R 20 and R 32"37 are each independently selected from H, C ⁇ -alkyl, C 2-6 - alkenyl, C 2 - 6 -alkynyl, aryl, C 1-6 -haloalkyl, and a linker group optionally attached to a solid support.
  • the compound of formula (I) is a compound of formula (VIII):
  • the complex of formula (I) is of formula (VIII) as defined above, wherein:
  • X " is an anion selected from CI " and TfO " ;
  • D is optional and is selected from (VI) and (VII),
  • R 3 and R 4 are each independently selected from H, C 1-6 -alkyl, aryl and C 1-6 -haloalkyl, and a linker group optionally attached to a solid support.
  • D is PPh 3
  • X " is OTf
  • the first step in the reaction is the loss of this ligand to form a precursor.
  • the precursor so formed is then capable of interacting with the substrate of formula (II).
  • the compound of formula (I) is a compound of formulas (IXa-IXb) selected from the following:
  • the complex of formula (I) is a compound of formula (X) selected from the following:
  • the compound of formula (I) is selected from the following:
  • the compound of formula (I) is selected from the following:
  • the complex of formula (I) is derived from a precursor that is a ⁇ - diketiminate-type ligand.
  • Deprotonation of the structure shown on the left below gives rise to a ⁇ -diketiminate-type ligand as shown on the right below, that is conventionally represented with the dashed lines showing a delocalisation of the negative charge.
  • the negative charge may of course be further delocalised over the molecule, depending on the nature of the A and B rings.
  • the ⁇ -diketiminate-type ligand is capable of forming a complex with Ru(ll), Os(ll) or
  • Fe(ll) for example, an r -arene ⁇ -diketiminato-ruthenium complex, an rf-arene ⁇ - diketiminato-osmium complex or an rf-arene ⁇ -diketiminato-iron complex.
  • the coordination between the metal M and the donor ligand D e.g., rf-arene is represented as a dashed line.
  • the complex of formula (I) is anchored to a solid support, for example, a polymer, thereby facilitating easy separation of the spent materials.
  • a solid support for example, a polymer
  • suitable solid supports will be familiar to one of ordinary skill in the art.
  • suitable linker groups for attaching the complex of formula (I) to the solid support will also be familiar to the skilled artisan.
  • the post-grafting of the catalyst to an insoluble solid surface is preferably achieved via attachment through one or more of the groups R 1 - R 20 , i.e. one or more of the groups R - R 20 is a linker group optionally attached to a solid support.
  • the insoluble solid surface is mesoporous silica, e.g. MC -41 containing hexagonal channels.
  • the complex of formula (I) is anchored to the solid surface via a linear silanol alkyl tether.
  • the complex of formula (I) may be prepared and isolated prior to use in the process of the invention, or may be generated in situ.
  • Another preferred embodiment of the invention relates to a complex selected from 6a- 6r and 1 1a to 1 1h as defined above. More preferably, the complex is selected from 6e- 6h, 6j, 6k and 11 a-f .
  • the process of the reaction is typically carried out using a suitable solvent system.
  • the substrate of formula (II) is dissolved or slurried in a polar, non-protic solvent.
  • suitable solvents include toluene, chlorinated and fluorinated solvents such as methylene chloride and 1 ,2-dichlorobenzene, and ethereal solvents such as tetrahydrofuran (THF), 1 ,2-dimethoxyethane, diglyme and polyethylene glycol dimethyl ether.
  • solvents may be used either individually or in combination with each other.
  • Particularly preferred solvents include THF, 1-butyl-3- methylimidazolium tetrafluoroborate (BmimBF 4 ), 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1- butyl-3-methylimidazolium chloride (BmimCI) and 1-butyl-3-methylimidazolium bromide (BmimBr).
  • Particularly preferred fluorinated solvents include ⁇ , ⁇ , ⁇ -trifluorotoluene.
  • the solvent is selected from THF, 1-butyl-3- methylimidazolium tetrafluoroborate (BmimBF 4 ), 1-butyl-3-methylimidazolium chloride (BmimCI) and 1-butyl-3-methylimidazolium bromide (BmimBr).
  • the process of the invention uses a non-volatile solvent, so that only dihydrogen is liberated during the reaction.
  • the process of the invention takes place in a homogeneous mixture, i.e. preferably the complex of formula (I) is essentially soluble in the reaction solvent(s) and remains essentially in solution through the reaction process with minimal amounts of precipitation.
  • the process takes place without additional solvent.
  • the substrate (II) is either liquid at the reaction temperature or in an mixture with the catalyst (I) or in a mixture of different substrates according to formula (II) due to melting point reduction in mixtures.
  • the solvent is a mixture of THF and dimethoxyethane.
  • the ratio of THF and dimethoxyethane is from about 4:1 to about 3:1.
  • the complex of formula (I) is dissolved or slurried in solution with the same solvent as that used to dissolve or slurry the substrate of formula (II).
  • the catalyst to substrate ratio directly controls the rate of hydrogen released.
  • the process of the invention is carried out at close to atmospheric pressure.
  • the process can be carried out without the need for an external heat source.
  • the process of the invention is carried out at a temperature of at least 0°C.
  • the process is carried out at room temperature (approximately 25°C).
  • the process is carried out at a temperature of from about 20°C to about 50°C, preferably from about 25°C to about 45°C, more preferably from about 30°C to about 45°C, more preferably still from about 35°C to about 45°C, even more preferably from about 40°C to about 45°C.
  • the process is carried out at a temperature of from about 50°C to about 80°C, preferably from about 60°C to about 80°C, more preferably from about 65°C to about 80°C, more preferably still from about 65°C to about 75°C, even more preferably from about 70°C to about 75°C.
  • the hydrogen that is generated in the process of the invention may be optionally captured using any known means.
  • the reaction may be performed in air, but may also be performed in an inert atmosphere, for example, under argon or neon, or under hydrogen.
  • the process of the invention is carried out in the absence of oxygen.
  • the process of the invention is carried out in an inert atmosphere.
  • the process of the invention can also be carried out in the presence of oxygen and/or water in the atmosphere.
  • the process of the invention is carried out in the presence of oxygen.
  • the process of the invention is carried out in the presence of oxygen and atmospheric water.
  • the process of the invention is used to generate hydrogen, which is supplied to a hydrogen fuel cell, such as a PEMFC.
  • Hydrogen generators may include a first compartment holding a catalyst-comprising solution and a second compartment holding the one or more substrates of formula (II) as defined above.
  • a further aspect of the invention therefore relates to a hydrogen generation system comprising:
  • X " is an anion
  • M is a metal selected from Ru, Os, Fe, Co and Ni;
  • D is optionally present and is one or more monodentate or multidentate donor iigands;
  • Y 1 is selected from CR 13 , B and N;
  • each of A and B is independently a saturated, unsaturated or partially unsaturated carbocyclic hydrocarbon ring;
  • R 3 and R 4 are each independently selected from H, C 1-6 -alkyl, aryl and C ⁇ e-haloalkyl, and a linker group optionally attached to a solid support; or
  • Y 2 is a direct single bond or double bond, or is CR 18 ;
  • R , R 2 , R 5"13 and R 6"18 are each independently selected from H, C 1-6 -alkyl, C 2-6 -alkenyl, C 2- 6-alkynyl, aryl, Ci -6 -haloalkyl, NR 19 R 20 and a linker group optionally attached to a solid support;
  • R 1 ⁇ 13 and R 16-18 groups are linked, together with the carbons to which they are attached, to form a saturated or unsaturated hydrocarbon group;
  • R 14 , R 15 , R 19 and R 20 are each independently selected from H, C -6 -alkyl, C 2 - 6 -alkenyl, C 2 .6-alkynyI, aryl, C 1-6 -haloalkyl, and a linker group optionally attached to a solid support;
  • R 21 to R 24 are each independently selected from H, C 1-6 -alkyl, fluoro- substituted C 1-6 -alkyl, C 6 . 14 -aryl and C 6 _i4-aralkyl, or any two of R 21 , R 22 , R 23 and R 24 are linked to form a C 3 .
  • a substrate comprising two, three or four substrates of formula (II) linked via one or more bridging groups so as to form a dimeric, trimeric or tetrameric species, and wherein the bridging group is selected from straight or branched C -6 -alkylene optionally substituted by one or more fluoro groups; boron; C 6-14 -aryl; and C 6-14 -aralkyl; or a substrate comprising two, three or four substrates of formula (II) which are joined so as to form a fused cyclic dimeric, trimeric or tetrameric species; and
  • the hydrogen generation system comprises a first compartment comprising the at least one complex of formula (I), a second compartment comprising the at least one substrate of formula (II), wherein the first or second compartment further comprises a solvent and/or a means for combining the contents of the first compartment with the contents of the second compartment such that when the contents are combined, hydrogen is generated.
  • the hydrogen generation system further comprises at least one flow controller to control a flow rate of the at least one complex of formula (I) or the at least one substrate of formula (II).
  • control electronics are coupled to substrate mass flow controllers and hydrogen mass flow controllers.
  • Mass flow controllers control the flow of the substrate solution, which enters the first compartment to achieve a desired hydrogen flow generated by the hydrogen generator.
  • the catalyst contained in the first compartment may be tethered to a surface by a linker.
  • the at least one substrate of formula (II) is stored in a separated compartment as a solid, a liquid or as a solution in a solvent.
  • control electronics send a signal to a mass flow controller (or a flow controller) to allow a predetermined flow rate of the at least one substrate of formula (II) in a solvent (or in its liquid form) in a second compartment to flow into the first compartment which holds the complex of formula (I).
  • a mass flow controller or a flow controller
  • the complex of formula (I) in the solvent can be provided in the second compartment and be pumped into the first compartment holding the substrate of formula (II).
  • the hydrogen generation system is preferably in the form of a self-contained reaction vessel that is attached via a vent to any application requiring a source of hydrogen gas, for example, a chemical reaction, a fuel cell, or the like.
  • Suitable fuel cells will be familiar to one skilled in the art and include any fuel cells that can use hydrogen as a fuel source, for example, internal combustion engines (ICE), solid oxide fuel cells (SOFC), phosphoric acid fuel cells (PAFC), alkaline fuel cells (AFC) and molten carbonate fuel cells (MCFC).
  • ICE internal combustion engines
  • SOFC solid oxide fuel cells
  • PAFC phosphoric acid fuel cells
  • AFC alkaline fuel cells
  • MCFC molten carbonate fuel cells
  • the hydrogen generation system is connected to a proton exchange membrane fuel cell (PEMFC). More preferably, a coupling connector delivers hydrogen generated by hydrogen generator to the anode of a PEMFC.
  • PEMFC proton exchange membrane fuel cell
  • the hydrogen generators disclosed herein are capable of delivering PEMFC grade hydrogen at low reaction temperatures, safely and reliably. Such hydrogen PEM fuel cells are optimal for applications where batteries and internal combustion engines do not deliver cost-effective and convenient power generation solutions.
  • the hydrogen generators disclosed herein provide a constant source of power in a compact size that does not require electrical recharging.
  • Another aspect of the invention relates to the use of at least one complex of formula (I) as defined above in a fuel cell.
  • Another aspect of the invention relates to a fuel cell comprising at least one complex of formula (I) as defined above.
  • the fuel cell further comprises a substrate of formula (II) as defined above, and optionally a suitable solvent.
  • Another aspect of the invention relates to a method of thermolytically dehydrogenating a substrate of formula (II) as described above, said method comprising contacting at least one substrate of formula (II) with a complex of formula (I) in the presence of a solvent.
  • Another aspect of the invention relates to the use of at least one complex of formula (I) as defined above in a method of thermolytically dehydrogenating a substrate of formula (II) as described above.
  • Another aspect of the invention relates to the use of at least one complex of formula (I) as defined above in a method of producing hydrogen.
  • the complex of formula (I) is used in conjunction with a substrate of formula (II) as defined above.
  • Another aspect of the invention relates to a method of using a hydrogen generation system as defined above which comprises modulating the hydrogen pressure in said system so as to modulate activity of the at least one complex of formula (I).
  • Figure 1 shows the results of a pressure reactor study of hydrogen equivalents released versus time (h), for the dehydrogenation of ammonia borane in THF at 42°C with (i) compound 6k, and (ii) catalyst 7.
  • the third trace is for the control experiment carried out in THF in the absence of catalyst.
  • Figure 2 shows the results of a pressure reactor study of hydrogen equivalents released versus time (h), for the dehydrogenation of ammonia borane in BmimBF 4 or BmimCI at 74°C with compound 6e versus controls.
  • Figure 3 shows the results of a pressure reactor study of hydrogen equivalents released versus time (h), for the dehydrogenation of DMAB in THF at room temperature with (i) compound 6e, (ii) compound 6k, and (iii) catalyst 7, versus control (absence of catalyst).
  • Figure 4 shows the results of a pressure reactor study of hydrogen equivalents released versus time (h), for the dehydrogenation of DMAB in THF at 42°C for catalysts 6e, 6g, 6j, 6k and catalyst 7 versus control (absence of catalyst).
  • Figure 5 shows the results of a pressure reactor study of hydrogen equivalents released versus time (h), for the solvent-free dehydrogenation of DMAB at 42°C with catalyst 6e and catalyst 7 versus control (absence of catalyst).
  • Figure 6 shows the results of a pressure reactor study of hydrogen equivalents released versus time (h), for the dehydrogenation of DMAB in THF at room temperature with catalyst 6e under non-protective atmosphere versus control (protective atmosphere, and absence of catalyst).
  • Figures 7a and 7b show the results of a pressure reactor study of hydrogen equivalents (based on the amounts of substrate) released versus time (h), for the dehydrogenation of DMAB in THF 42°C with catalyst 6e under addition of further aliquots of DMAB/THF solution.
  • Figure 8 shows the structure of (n 6 -benzene)-ruthenium(ll)-K 2 /V,/ ⁇ / , -/ ⁇ /,/ ⁇ /'-bis(2- methylthiophenyl)-1 ,3-diketiminato chloride (6a).
  • Figure 9 shows the structure of (r) 6 -benzene)-ruthenium(ll)- K 2 A/,/ ⁇ /'-/ ⁇ /,W-bis(2- methylthiophenyl)-1 ,3-diketiminato trifluoromethanesulfonate (6e). The anion is omitted for clarity.
  • Figure 10 shows the results of a pressure reactor study of hydrogen equivalents released versus time (h), for the dehydrogenation of DMAB in THF at 42°C for catalysts 11 a, 11 c, 11 d, 11 e, 1f and catalyst 7 versus control (absence of catalyst).
  • Acetylacetone (1.14 ml_, 11.1 mmol) and p-toluenesulfonic acid monohydrate (4.23 g, 22.2 mmol) were added to a 3-neck round-bottom flask with a Dean-Stark apparatus connected.
  • Degassed toluene (150 mL) and 2-methylthioaniline 1a (3.35 ml_, 26.75 mmol) were added to give a green solution, and the mixture refluxed at 150°C for 24 hours.
  • the resulting yellow solution was cooled, and solvent removed.
  • the resulting oil was taken up in dichloromethane (100 ml) and stirred with a solution of sodium carbonate (40 g in 100 ml H 2 0) for 30 minutes.
  • Lithium N, N'-bis( 2-ethylthiophenyl)-1 , 3-diketiminate 2b (3.0g, 8.1 mmol) was added to a dried Schlenk. Dry degassed pentane was transferred via cannula, and the pale yellow mixture cooled on ice. n-BuLi (6.0 mL, 1.6M in hexanes) was added dropwise to give a bright red mixture. After stirring for 3 hours at room temperature, the resulting solid was filtered, washed with dry pentane and dried to give 5b as an orange powder (1.67g, 55%).
  • the donor ligand D dissociates in (ref. structure II) solution to form the active catalytic species, although at some point re- association cannot be ruled out.
  • Some of the compounds (ref. Example 14, 16, 17) are isolated after synthesis as a mixture of the complex with the donor ligand D and the complex where D has been lost. These mixtures were used without further separation in the dehydrogenation experiments.
  • Crystals suitable for x-ray were grown by slow diffusion (THF).
  • THF slow diffusion
  • the NMR for this complex shows two species, one containing the coordinated benzene ring (6e), and one where benzene has been lost (6f). Percentage yield based on complex 6e. Crystals suitable for x-ray were grown by slow diffusion of dichloromethane into a pentane solution of 6e.
  • the volume of the filtrate was reduced, under vacuum, to 2 mL, and 25 mL of n-pentane was added to precipitate a purple-colored microcrystalline powder.
  • the solution was decanted from the solid, dried under vacuum for several hours and kept under glove box.
  • the yield of the purple complex 6k was 95% (340 mg, 0.398 mmol).
  • Example 26 Dehydrogenation of Ammonia Borane in THF with catalyst 6k at 42°C ( Figure 1 )
  • a 100 mL Parr 100 bar stainless steel pressure reactor fitted with an inlet valve (Swagelok SS-ORM2), release valve (Swagelok SS-43GS4), thermocouple, rupture disc, stirrer shaft (Parr A1 120HC5), and a 0-100 bar pressure gauge (Impress Sensors & Systems) connected to a Parr 4842 controller unit, was used for the experiment.
  • an inlet valve Swagelok SS-ORM2
  • release valve Swagelok SS-43GS4
  • thermocouple rupture disc
  • stirrer shaft Parr A1 120HC5
  • a 0-100 bar pressure gauge Impress Sensors & Systems
  • H 2 equivalents respectively to AB substrate were calculated from the recorded pressure data assuming ideal gas behaviour, assuming a total reactor volume (including head space) of 84 mL.
  • the Parr pressure reactor was flushed with nitrogen and preheated to 42°C using an oil bath prior to the start of the experiment.
  • a glass liner was filled with 0.5 g (16 mmol) of ammonia borane and 0.5 mol% (0.08 mmol, 69 mg) of 6k under a stream of N 2 , inserted into the reactor, and the reactor was sealed. 5 mL of dried/N 2 saturated THF were added through the sampling valve via a gas-tight syringe and the valve was closed.
  • the Parr pressure reactor was preheated to 74°C.
  • a glass liner was filled with 0.5 mol% (0.06 mmol, 42 mg) of 6e under a stream of N 2 , inserted into the reactor, and the reactor was sealed.
  • the Parr pressure reactor was preheated to 74°C.
  • a glass liner was filled with 0.5 mol% (0.06 mmol, 42 mg) 6e, ammonia borane (0.39 g, 12.7 mmol), and dry 1-butyl-1-methylimidazolium chloride (4 g) under a stream of N 2 , inserted into the reactor, and the reactor was sealed.
  • a glass liner was filled with DMAB (0.95 g, 16.2 mmol), under a stream of N 2 , inserted into the reactor, and the reactor was sealed.
  • a solution of 0.5 mol% (0.08 mmol, 54 mg) 6e in 5 mL of dried/N 2 saturated THF was added through the sampling valve via a gas-tight syringe and the valve was closed.
  • a glass liner was filled with DMAB (0.95 g, 16.2 mmol) and 0.5 mol% (0.08 mmol, 69 mg) 6k under a stream of N 2 , inserted into the reactor, and the reactor was sealed. 5 mL of dried/N 2 saturated THF was added through the sampling valve via a gas-tight syringe and the valve was closed.
  • Example 35 Solvent-free dehydrogenation of DMAB at 42°C with catalyst 6e ( Figure 5)
  • Example 36 Dehydrogenation of DMAB in THF at room temperature with catalyst 6e under non-protective atmosphere ( Figure 6)
  • Acetylacetone (0.96 g, 9.59 mmol) and p-toluenesulfonic acid monohydrate (2.00 g, 10.5 mmol) were added to a 3-neck round-bottom flask with a Dean-Stark apparatus connected.
  • Degassed toluene (150 mL) and 4-methyl-2-(methylthio)aniline 8 (2.88 g, 18.67 mmol) were added to give a green solution, and the mixture refluxed at 150°C for 24 hours.
  • the resulting yellow solution was cooled, and solvent removed.
  • the resulting oil was taken up in dichloromethane (100 ml) and stirred with a solution of sodium carbonate (40 g in 100 ml H20) for 30 minutes.
  • the NMR for this complex shows two species, one containing the coordinated benzene ring (11a), and one where benzene has been lost (11 b). Percentage yield based on complex 11a. Each of the species occurs in different stereoisomers yielding a highly complex 1 H NMR spectrum.
  • the NMR for this complex shows two species, one containing the coordinated hexamethylbenzene ring (11c), and one where hexamethylbenzene has been lost (6f). Percentage yield based on complex 11c. Each of the species occurs in different stereoismoers yielding a highly complex 1 H NMR spectrum.
  • Crystals suitable for x-ray were grown by slow diffusion (THF).
  • THF slow diffusion
  • the NMR for this complex shows two species, one containing the coordinated benzene ring (11g), and one where benzene has been lost (11 h). Percentage yield based on complex 11g.

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Abstract

La présente invention concerne un procédé pour la production d'hydrogène comprenant la mise en contact d'au moins un complexe de formule (I), (I) dans laquelle : X- représente un anion; M est un métal choisi parmi Ru, Os, Fe, Co et Ni; D est facultativement présent et est un ou plusieurs ligands donneurs monodentates ou multidentates; Y1 est choisi parmi CR13, B et N; Z1 et Z2 sont chacun indépendamment choisis parmi =N, =P, NR14, PR15, O, S et Se; ou Z2 est une liaison directe entre le noyau carbocyclique B et le substituant R4; chacun parmi A et B représente indépendamment un noyau hydrocarboné carbocyclique saturé, insaturé ou partiellement insaturé; R3 et R4 sont chacun indépendamment choisis parmi H, alkyle en C1-6, aryle et haloalkyle en C1-6, et un groupe de liaison facultativement fixé à un support solide; ou R3 et R4 forment conjointement la fraction suivante : (AB) Y2 est une liaison simple ou double liaison directe ou représente CR18; R1, R2, R5-13 et R16-18 sont chacun indépendamment choisis parmi H, alkyle en C1-6, alcényle en C2-6, alcynyle en C2-6, aryle, haloalkyle en C1-6, NR19R20 et un groupe de liaison facultativement fixé à un support solide; ou au moins deux parmi lesdits groupes R1-13 et R16-18 sont liés, conjointement avec les carbones auxquels ils sont fixés, pour former un groupe hydrocarboné saturé ou insaturé; R14, R15, R19 et R20 sont chacun indépendamment choisis parmi H, alkyle en C1-6, alcényle en C2-6, alcynyle en C2-6, aryle, haloalkyle en C1-6, et un groupe de liaison facultativement fixé à un support solide; avec au moins un substrat de formule (II), R21R22NH-BHR23R24, où R21 à R24 sont chacun indépendamment choisis parmi H, alkyle en C1-6, alkyle en C1-6 substitué par fluoro, aryle en C6-14 et aralkyle en C6-14, ou n'importe quels deux éléments parmi R21, R22, R23 et R24 sont liés pour former un groupe alkylène en C3-10 ou un groupe alcénylène en C3-10, qui conjointement avec les atomes d'azote et/ou de bore auxquels ils sont fixés, forment un groupe cyclique; ou un substrat comprenant deux, trois ou quatre substrats de formule (II) liés par l'intermédiaire d'un ou plusieurs groupes pontants de façon à former une espèce dimérique, trimérique ou tétramérique, et où le groupe pontant est choisi parmi alkylène en C1-6 linéaire ou ramifié facultativement substitué par un ou plusieurs groupes fluoro, bore, aryle en C6-14 et aralkyle en C6-14; ou un substrat comprenant deux, trois ou quatre substrats de formule (II) qui sont joints de façon à former une espèce dimérique, trimérique ou tétramérique cyclique fusionnée. D'autres aspects de l'invention concernent un système de génération d'hydrogène comprenant un complexe de formule (I), un substrat de formule (II) et un solvant, et l'utilisation de complexes de formule (I) dans des piles à combustible. Un autre aspect de l'invention concerne de nouveaux complexes de formule (I).
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US10707531B1 (en) 2016-09-27 2020-07-07 New Dominion Enterprises Inc. All-inorganic solvents for electrolytes
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